Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B56/00—Azo dyes containing other chromophoric systems
  • C09B56/14—Phthalocyanine-azo dyes

Definitions

• the present invention relates to novel, water-soluble phthalocyanine compounds, processes for their preparation and their use for dyeing and printing fibre materials, in particular textile fibre materials.
• the present invention relates to novel, water-soluble phthalocyanine compounds of the formula ##STR2## in which R 1 and R 2 are identical or different and in each case are hydrogen, hydroxyalkyl having 2 to 5 carbon atoms or carboxyalkyl having 1 to 5 carbon atoms in the alkyl radical or phenyl, or R 1 and R 2 , together with the nitrogen atom, are a heterocyclic ring which can contain further hetero atoms, R 3 is hydrogen or methyl, R 4 is alkyl or alkoxy each of which has 1 to 5 carbon atoms, --NHCOR 6 in which R 6 is alkyl or hydroxyalkyl having in each case 1 to 3 carbon atoms, or substituted or unsubstituted phenyl, or sulfo, R 5 is alkyl or alkoxy each of which has 1 to 5 carbon atoms, hydroxyl, carboxyl or sulfo, at least two substituents R 5 which are different from one another being present in the pheny
• the substituents R 1 and R 2 which are identical or different from one another, are hydrogen, hydroxyalkyl having 2 to 5 carbon atoms, for example hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl and hydroxy-n-pentyl, and the corresponding branched hydroxyalkyl radicals; carboxyalkyl having 1 to 5 carbon atoms in the alkyl moiety, for example carboxymethyl, carboxyethyl, carboxy-n-propyl, carboxy-n-butyl or carboxy-n-pentyl, and the corresponding carboxyalkyl radicals in which the alkyl moiety is branched; or phenyl.
• Preferred substituents R 1 and R 2 are hydrogen; hydroxyethyl or carboxyalkyl having 1 or 2 carbon atoms in the alkyl radical (--CH 2 COOH or --CH 2 CH 2 COOH) or phenyl, and, as a particularly preferred combination, one of the substituents R 1 or R 2 is hydrogen and the other is one of the substituents indicated.
• R 1 and R 2 together with the nitrogen atom to which they are attached, form a heterocyclic ring, these are preferably saturated heterocyclic 5-membered or 6-membered rings which can contain, as further hetero atoms, nitrogen, sulfur and/or oxygen atoms.
• heterocyclic radicals --NR 1 R 2 are thus pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or piperazino, pyrrolidino, piperidino, morpholino and thiomorpholino being preferred.
• R 3 is methyl or, preferably, hydrogen.
• R 4 and R 5 as C 1 -C 5 alkyl in the compounds of the formula (1): methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or isopentyl.
• the said alkyl radicals which have 1 to 3 carbon atoms, in particular methyl, are preferred.
• R 4 and R 5 as C 1 -C 5 -alkoxy: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy or isopentoxy.
• the said alkoxy radicals which have 1 to 3 carbon atoms, in particular methoxy, are preferred.
• R 4 as --NHCOR 6 in the compounds of the formula (1) are substituents such as --NHCOCH 3 , --NHCOCH 2 CH 3 , --NHCOCH 2 CH 2 CH 3 , --NHCOCH 2 OH, --NHCOCH 2 CH 2 OH, --NHCOCH 2 CH 2 CH 2 OH or ##STR3## in which the phenyl ring can be unsubstituted or substituted, for example by methyl or halogen.
• Preferred substituents --NHCOR 6 are --NHCOCH 3 , --NHCOCH 2 OH or --NHCOC 6 H 5 .
• substituents R 4 and R 5 the meaning sulfo embraces both the free acid form (--SO 3 H) and the salt form, alkali metal salts (Li, Na or K) or ammonium salts being particularly suitable.
• R 5 are hydroxyl or carboxyl (--COOH), there being at least two substituents which are different from one another present in ring A, for example 2 to 4 or, preferably, 2 or 3 of these substituents, for example hydroxyl and carboxyl.
• p is accordingly a number from 2 to 4 and is preferably 2 or 3.
• the radical ##STR4## is located, for example, in the meta-position, preferably in the para-position, relative to the group ##STR5##
• Me as a metal atom attached by coordination in the compounds of the formula (1) are an iron, cobalt, nickel atom and especially a copper atom.
• Pc is short for a (a+b+c)-valent phthalocyanine radical.
• the indices a and c preferably have in each case an (average) value of 1 to 1.5, particularly preferably in each case a value of approx. 1; the index b preferably has an (average) value of 0.5 to 1.
• the total of the indices (a+b) particularly preferably has an (average) value ⁇ 2, especially a value of 1.5.
• Preferred compounds of the formula (1) are those in which R 1 and R 2 are identical or different from one another and are in each case hydrogen, hydroxyethyl or carboxyalkyl having 1 or 2 carbon atoms in the alkyl radical, or phenyl, or R 1 and R 2 , together with the nitrogen atom, are a heterocyclic 5-membered or 6-membered ring which can contain, as further hetero atoms, nitrogen, sulfur and/or oxygen atoms, R 4 is alkyl or alkoxy having in each case 1 to 3 carbon atoms, --NHCOCH 3 , --NHCOCH 2 OH, --NHCOC 6 H 5 or sulfo, R 5 is alkyl or alkoxy having 1 to 3 carbon atoms, hydroxyl, carboxyl or sulfo, there being two or three substituents R 5 , of which at least two are different from one another, present in the phenyl ring A, and Me is an iron, cobalt, nickel and especially copper atom which is attached
• R 1 and R 2 are identical or different from one another and are in each case hydrogen, hydroxyethyl or carboxyalkyl having 1 or 2 carbon atoms in the alkyl radical, or phenyl, or R 1 and R 2 , together with the nitrogen atom, are a heterocyclic 5-membered or 6-membered ring which can contain, as further hetero atoms, nitrogen, sulfur and/or oxygen atoms
• R 4 is alkyl or alkoxy having in each case 1 to 3 carbon atoms, --NHCOCH 3 , --NHCOCH 2 OH, --NHCOC 6 H 5 or sulfo
• R 5 is alkyl or alkoxy having 1 to 3 carbon atoms, hydroxyl, carboxyl or sulfo, there being two or three substituents R 5 , of which at least two are different from one another, present in the phenyl ring A, and Pc, R 3 ,
• the process according to the invention is preferably carried out at 0° to 40° C. and at a pH within the range from 5 to 8.
• Suitable condensation aids are compounds containing nitrogen, for example pyridine, nicotinic acid or imidazole.
• the compounds of the formulae (4) and (5) can be reacted simultaneously or successively with the phthalocyaninesulfochlorides of the formula (3), the latter as a rule being first reacted with the azo dyes of the formula (4) containing amino groups and then with the amines of the formula (5).
• These compounds are employed in b-fold or c-fold molar amounts, relative to the compound of the formula (3), and preferably also in a 0.1-fold to 1-fold molar excess.
• the alkaline hydrolysis can be carried out using alkali metal hydroxides, carbonates or bicarbonates or ammonia or amines; the acid hydrolysis can be carried out using mineral acids, in particular hydrochloric or sulfuric acid.
• a further possible means of preparing the compounds of the formula (1) consists in reacting the phthalocyaninesulfochlorides of the formula (3) with a compound of the formula ##STR10## detaching the protective group R 7 , for example acetyl, by hydrolysis, diazotizing the resulting amino group and then coupling the product with a coupling component of the formula ##STR11##
• reaction with the compound of the formula (5) can then be carried out at the same time as the reaction with the compound of the formula (6), or subsequent to the coupling reaction.
• the phthalocyaninesulfochlorides of the formula (3) which are used as starting compounds are known to those skilled in the art or can be prepared by processes known per se (reacting the metal phthalocyanine with chlorosulfonic acid and/or thionyl chloride at an elevated temperature) (see, for example, K. Venkataraman, The Chemistry of synthetic dyes, Volume V, page. 261 (1971), Academic Press, New York/London; F. M. Moser, A. L. Thomas, The phthalocyanines, Volume II, pages 20-22, CRC Press; 1983).
• the compounds of the formula (4) are similarly known azo dyes, as a rule yellow azo dyes, having a free primary or secondary amino group.
• the amino compounds of the formula (5) are generally known and are readily accessible.
• the present invention also relates to the use of the phthalocyanine compounds of the formula (1), and also, if appropriate, mixtures of these compounds, for dyeing or printing fibre materials containing nitrogen and particularly fibre materials containing hydroxyl groups.
• phthalocyanineazo dyes of the formula (1) are thus suitable for dyeing and printing fibre materials containing nitrogen or especially cellulosic fibre materials, preferably textile fibre materials composed of silk, wool or synthetic polyamides, and preferably composed of the cellulosic fibres, such as rayon, cotton or hemp.
• the textile fibre materials can be in a very wide variety of processing states, for example as fibre, yarn, woven fabric or knitted fabric.
• Level dyeings are obtained in brilliant green colour shades having good overall fastness properties, in particular good fastness properties to rubbing, wet processing, wet rubbing, perspiration and light. If necessary, the wet fastness properties, in particular the fastness to washing, of the resulting direct dyeings and prints can be improved appreciably by an after-treatment with so-called fixing agents.
• the dyes, according to the invention, of the formula (1) can readily be combined with other dyes, in particular disperse dyes.
• the dyes according to the invention exhibit an adequate stability to high temperatures and can thus be used for dyeing under the dyeing conditions for polyester fibres, i.e. at temperatures in the range from about 100° to 150° C., preferably from 110° to 130° C., from an aqueous liquor and at a pH of 4 to 7.5, preferably 5 to 7.
• the provision of the dyes, according to the invention, of the formula (1) makes it possible to simplify considerably the dyeing of textile mixed fibres (mixed fabrics), for example those composed of polyester and cellulose fibres.
• the dyeing, customary per se, of each type of fibre in a mixture of fibres in a separate operation using different dyeing conditions is thus no longer necessary.
• the compounds, according to the invention, of the formula (1) are also suitable for the preparation of aqueous inks for ink jet printing.
• Parts and percentages are by weight, unless stated otherwise. Parts by weight and parts by volume are in the same relation to one another as kilograms and liters. The temperatures are quoted in degrees centigrade.
• the resulting dye is precipitated by means of 15 g of sodium chloride and is filtered off and washed first with 5% aqueous sodium chloride solution and then with ethanol until a colourless filtrate is obtained.
• the dyes of the formulae ##STR13## can also be prepared analogously.
• the dye is salted out by means of sodium chloride, filtered off, washed first with sodium chloride solution and then with ethanol and dried.
• the resulting dye of the formula ##STR15## dyes cellulose and leather in brilliant bluish-tinged green shades of good fastness to light.
• the pH is kept at a value of 8.5 to 8.7 during the reaction by adding 2N aqueous ammonia solution.
• the resulting dyestuff is salted out by means of sodium chloride, filtered off and washed first with aqueous sodium chloride solution and then with ethanol. 60 parts of the crude dye of the formula ##STR16## are obtained after drying.
• the dye dyes cellulose materials and leather in brilliant green shades of good fastness to light and, in particular after an after-treatment with cationic fixing agents, good wet fastness properties.
• the suspension of the diazonium salt is then added dropwise at 0° to 4° C. to a solution of 22.9 parts of salicylic acid (sodium salt) in 200 parts of ice-water.
• the pH of the reaction mixture is kept at a value of approx. 8.5 during the coupling reaction by adding 30% sodium hydroxide solution.
• sodium chloride is added to the reaction solution, and the dye which has been salted out is filtered off, washed with sodium chloride solution and dried. This gives the dyestuff of the formula ##STR18## which dyes cellulose materials and leather in bluish-tinged, brilliant green shades of good fastness to light.
• a fibre mixture composed of polyester and cotton 10 parts are introduced at approx. 50° C. into a dyebath containing 200 parts of water, a mixture of dyes consisting of 0.05 part of C.I. Disperse Yellow 99, 0.5 part of C.I. Disperse Blue 60 and 0.2 part of the dye according to Example 2, 0.4 part of ammonium sulfate and 0.2 part of an anionic dispersing agent (for example the formaldehyde condensation product of naphthalenesulfonic acid).
• the pH of the dyebath is adjusted to a value of 5.5 with formic acid, 1 part of sodium sulfate decahydrate is added and the dyebath is then heated to approx. 130° C. in the course of 45 minutes.
• Dyeing is continued for a further 45 minutes at 130° C. and the dyebath is then cooled to approx. 80° C. in the course of 30 minutes and is kept at this temperature for a further 45 minutes. The dyeing is then thoroughly rinsed with cold water and is dried.
• Dyeing Instructions 1 or 2 The procedure described in Dyeing Instructions 1 or 2 is repeated, except that after the conclusion of the dyeing process the dyeing is put, after cold rinsing, into a fresh bath warmed to approx. 30° C. and containing 200 parts of water and 0.2-0.6 part of a cationic after-treatment agent (an amine-formaldehyde-dicyandiamide condensation product or a formulation based on dicyandiamide and diethylenetriamine).
• a cationic after-treatment agent an amine-formaldehyde-dicyandiamide condensation product or a formulation based on dicyandiamide and diethylenetriamine.
• Dyeing instructions 1 or 2 The procedure described in Dyeing instructions 1 or 2 is repeated, except that after the conclusion of the dyeing process the dyeing is put, after cold rinsing, into a fresh bath, warmed to approx. 25° C. and containing 200 parts of water, 1 part of sodium sulfate decahydrate and 0.6 part of a fibre-reactive, cationic after-treatment agent based on an N-methyldialkylamine and epichlorohydrin. The temperature is raised to 40° C. in the course of 15 minutes, 0.8 part of 30% sodium hydroxide solution is added and the dyeing is subjected to treatment for a further 45 minutes at 40° C. The dyeing is finally given a hot rinse and dried; it has improved wet fastness properties.

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• Nitrogen Condensed Heterocyclic Rings (AREA)

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• 1989
  • 1989-05-01 ES ES89810337T patent/ES2058590T3/es not_active Expired - Lifetime
  • 1989-05-01 EP EP89810337A patent/EP0342158B1/de not_active Expired - Lifetime
  • 1989-05-01 DE DE89810337T patent/DE58905414D1/de not_active Expired - Fee Related
  • 1989-05-03 US US07/346,689 patent/US5059682A/en not_active Expired - Fee Related
  • 1989-05-10 MX MX1598189A patent/MX15981A/es unknown
  • 1989-05-10 BR BR898902190A patent/BR8902190A/pt not_active IP Right Cessation
  • 1989-05-10 KR KR1019890006224A patent/KR0148686B1/ko not_active IP Right Cessation
  • 1989-05-11 JP JP1116216A patent/JP2703051B2/ja not_active Expired - Fee Related
  • 1989-05-12 AR AR89313871A patent/AR246978A1/es active

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